CN115305297B - A kind of synthetic fatliquoring agent and its preparation method and application - Google Patents
A kind of synthetic fatliquoring agent and its preparation method and application Download PDFInfo
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- CN115305297B CN115305297B CN202211069151.3A CN202211069151A CN115305297B CN 115305297 B CN115305297 B CN 115305297B CN 202211069151 A CN202211069151 A CN 202211069151A CN 115305297 B CN115305297 B CN 115305297B
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- fatting
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- mixing
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- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- -1 trimethylolpropane fatty acid ester Chemical class 0.000 claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 51
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010985 leather Substances 0.000 claims abstract description 37
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 34
- 239000000194 fatty acid Substances 0.000 claims abstract description 34
- 229930195729 fatty acid Natural products 0.000 claims abstract description 34
- 238000005886 esterification reaction Methods 0.000 claims abstract description 33
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 32
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000539 dimer Substances 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 20
- 239000006184 cosolvent Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 238000002156 mixing Methods 0.000 claims description 46
- 239000011976 maleic acid Substances 0.000 claims description 25
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 24
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 24
- 239000003899 bactericide agent Substances 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 15
- 230000000844 anti-bacterial effect Effects 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 229930182478 glucoside Natural products 0.000 claims description 5
- BTGGRPUPMPLZNT-PGEUSFDPSA-N 2,2-bis[[(z)-octadec-9-enoyl]oxymethyl]butyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC BTGGRPUPMPLZNT-PGEUSFDPSA-N 0.000 claims description 4
- RKJGFHYCZPZJPE-UHFFFAOYSA-N 2,2-bis(16-methylheptadecanoyloxymethyl)butyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCCCCCCCCCC(C)C)COC(=O)CCCCCCCCCCCCCCC(C)C RKJGFHYCZPZJPE-UHFFFAOYSA-N 0.000 claims description 3
- PDDAEITXZXSQGZ-UHFFFAOYSA-N 2,2-bis(octadecanoyloxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC PDDAEITXZXSQGZ-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229940118594 trimethylolpropane triisostearate Drugs 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 230000032050 esterification Effects 0.000 abstract description 7
- 102000008186 Collagen Human genes 0.000 abstract description 5
- 108010035532 Collagen Proteins 0.000 abstract description 5
- 229920001436 collagen Polymers 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 20
- 239000003429 antifungal agent Substances 0.000 description 17
- 229940121375 antifungal agent Drugs 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000002191 fatty alcohols Chemical class 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 229920000136 polysorbate Chemical class 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 230000000855 fungicidal effect Effects 0.000 description 5
- 239000000417 fungicide Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 229940043810 zinc pyrithione Drugs 0.000 description 4
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical group [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003020 moisturizing effect Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229940001584 sodium metabisulfite Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000011078 sorbitan tristearate Nutrition 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035943 smell Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- 239000001589 sorbitan tristearate Substances 0.000 description 2
- 229960004129 sorbitan tristearate Drugs 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- GFGVSDNYVNXQRK-UEQSERJNSA-N (2R,3R,4S,5R)-1,2,3,4,5-pentahydroxytetracosan-6-one Chemical compound CCCCCCCCCCCCCCCCCCC(=O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO GFGVSDNYVNXQRK-UEQSERJNSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KBEFBSGNGSLHOD-UHFFFAOYSA-N 4-methylpentane-1,1-diol Chemical compound CC(C)CCC(O)O KBEFBSGNGSLHOD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid ester group Chemical group C(CCCCCCCCCCC)(=O)O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- TXGJTWACJNYNOJ-UHFFFAOYSA-N hexane-2,4-diol Chemical compound CCC(O)CC(C)O TXGJTWACJNYNOJ-UHFFFAOYSA-N 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 description 1
- 229940048848 lauryl glucoside Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- NRTBZBYBLPEOCE-UHFFFAOYSA-L potassium;sodium;sulfite Chemical compound [Na+].[K+].[O-]S([O-])=O NRTBZBYBLPEOCE-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
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Abstract
本发明提供了一种合成加脂剂及其制备方法和应用，涉及皮革助剂技术领域。本发明提供的合成加脂剂包括第一加脂活性组分(制备原料包括三羟甲基丙烷脂肪酸酯、乙醇胺、顺丁烯二酸酐、pH调节剂和亚硫酸根)、第二加脂活性组分(制备原料包括山梨醇酐酯类化合物、顺丁烯二酸酐、pH调节剂和亚硫酸根)、第三加脂活性组分(二聚酸与聚乙二醇的酯化产物)、乳化剂、助溶剂和水。本发明提供的合成加脂剂中含有氨基、羟基、羧基和双键多种活性官能团，与皮革胶原纤维的结合力强，能够显著提高皮革的柔软度、抗撕力以及皮革对于的合成加脂剂吸收率。而且，本发明提供的合成加脂剂应用于皮革中时，不产生三废，绿色环保。The invention provides a synthetic fatliquoring agent and its preparation method and application, and relates to the technical field of leather auxiliaries. The synthetic fatliquoring agent provided by the present invention comprises the first fatliquor active component (preparation raw material comprises trimethylolpropane fatty acid ester, ethanolamine, maleic anhydride, pH regulator and sulfite), the second fatliquor Active component (preparation raw materials include sorbitan ester compound, maleic anhydride, pH regulator and sulfite), third fatliquor active component (esterification product of dimer acid and polyethylene glycol) , emulsifier, co-solvent and water. The synthetic fatliquoring agent provided by the present invention contains multiple active functional groups such as amino, hydroxyl, carboxyl and double bonds, has a strong binding force with leather collagen fibers, and can significantly improve the softness, tear resistance and synthetic fatliquoring of leather. agent absorption rate. Moreover, when the synthetic fatliquoring agent provided by the invention is applied to leather, it does not produce three wastes and is environmentally friendly.
Description
技术领域technical field
本发明涉及皮革助剂技术领域，具体涉及一种合成加脂剂及其制备方法和应用。The invention relates to the technical field of leather auxiliary agents, in particular to a synthetic fatliquoring agent and its preparation method and application.
背景技术Background technique
加脂是制革生产中至为关键的工序，通过对皮革进行合理适当的加脂，让其吸收适量的加脂材料，使皮革胶原纤维得以充分疏松，恢复皮革原来的柔软度和弹性，防止皮革僵硬发板、开裂，赋予皮革以一定的使用性能。皮革通过加脂作用，其抗张强度、韧性、延伸率、得革率等有所提高，还赋予了皮革良好的手感。Fatliquoring is the most critical process in tanning production. Reasonable and appropriate fatliquoring is carried out on the leather to allow it to absorb an appropriate amount of fatliquoring materials, so that the collagen fibers of the leather can be fully loosened, and the original softness and elasticity of the leather can be restored. The leather is stiff, plated and cracked, which endows the leather with certain performance. Through fatliquoring, the tensile strength, toughness, elongation and leather yield of leather are improved, and the leather has a good feel.
常用的皮革加脂剂多数是天然动植物油脂通过乳化剂乳化，或经过化学改性，使其具备自乳化能力，常见的化学改性方法有磺化、氯磺化、硫酸化、氧化亚硫酸化、磷酸化以及醇解再酯化等。然而，硫酸化改性由于使用过量硫酸，需要用大量饱和食盐水洗涤，因而产生大量高盐酸水；氧化亚硫酸化改性则产生大量的VOC且气味较大；磷酸化改性产品使用时残留在废水中造成富磷化，这些改性方法均会对环境造成污染。而且，天然油脂较容易在空气中氧化产生酸败，水解等现象，易造成加脂剂产品质量，使用后皮革气味较大。Most of the commonly used leather fatliquoring agents are natural animal and vegetable oils emulsified by emulsifiers, or chemically modified to make them self-emulsifying. Common chemical modification methods include sulfonation, chlorosulfonation, sulfation, and oxidized sulfurous acid Phosphorylation, alcoholysis and re-esterification, etc. However, due to the use of excess sulfuric acid in the sulfation modification, it needs to be washed with a large amount of saturated brine, thus producing a large amount of high hydrochloric acid water; the oxidative sulfitation modification produces a large amount of VOC and has a strong smell; Phosphorization is caused in wastewater, and these modification methods will pollute the environment. Moreover, natural oils are more likely to oxidize in the air to produce rancidity, hydrolysis and other phenomena, which will easily cause the quality of the fatliquor product, and the leather smells stronger after use.
合成加脂剂因对皮革的加脂效果好、稳定性高，得到广泛应用。例如，以矿物油、硅油、油酸乙二醇酯、氯化石蜡和烷基磺酰胺等为原料或进行化学改性而制得的合成加脂剂，以及以长链丙烯酸酯、长链马来酸酯等为原料的聚合物型合成加脂剂。然而，上述合成加脂剂处理后的皮革的柔软度不够高。Synthetic fatliquor is widely used because of its good fatliquoring effect and high stability on leather. For example, synthetic fatliquor made from mineral oil, silicone oil, ethylene glycol oleate, chlorinated paraffin and alkylsulfonamide, etc., or chemically modified, and long-chain acrylate, long-chain horse Polymer type synthetic fatliquoring agent made from esters of toric acid. However, the suppleness of the above-mentioned synthetic fatliquor-treated leather is not high enough.
发明内容Contents of the invention
有鉴于此，本发明的目的在于提供一种合成加脂剂及其制备方法和应用，本发明提供的合成加脂剂能够显著提高皮革的柔软度。In view of this, the object of the present invention is to provide a synthetic fatliquoring agent and its preparation method and application. The synthetic fatliquoring agent provided by the present invention can significantly improve the softness of leather.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种合成加脂剂，包括以下质量份数的制备原料：第一加脂活性组分15～50份，第二加脂活性组分5～25份，第三加脂活性组分5～25份，乳化剂0～15份，助溶剂0～15份和水0～200份；The invention provides a synthetic fatliquoring agent, which comprises the following preparation raw materials in parts by mass: 15-50 parts of the first fatliquoring active component, 5-25 parts of the second fatliquoring active component, 5-25 parts of the third fatliquoring active component 5 to 25 parts, 0 to 15 parts of emulsifier, 0 to 15 parts of cosolvent and 0 to 200 parts of water;
所述第一加脂活性组分的制备原料包括三羟甲基丙烷脂肪酸酯、乙醇胺、顺丁烯二酸酐、pH调节剂和亚硫酸根；The raw materials for the preparation of the first fatliquoring active component include trimethylolpropane fatty acid ester, ethanolamine, maleic anhydride, pH regulator and sulfite;
所述第二加脂活性组分的制备原料包括山梨醇酐酯类化合物、顺丁烯二酸酐、pH调节剂和亚硫酸根；The raw materials for the preparation of the second fatliquoring active component include sorbitan ester compounds, maleic anhydride, pH regulator and sulfite;
所述第三加脂活性组分为二聚酸和聚乙二醇的酯化产物。The third fatliquoring active component is the esterification product of dimer acid and polyethylene glycol.
优选地，所述第一加脂活性组分的制备原料中，三羟甲基丙烷脂肪酸酯、乙醇胺、顺丁烯二酸酐、亚硫酸酸源中亚硫酸根摩尔比为1：(0.9～1.1)：(0.9～1.1)：(0.9～1.1)。Preferably, in the raw materials for the preparation of the first fatliquoring active component, the molar ratio of sulfite in trimethylolpropane fatty acid ester, ethanolamine, maleic anhydride, and sulfurous acid source is 1:(0.9～ 1.1): (0.9～1.1): (0.9～1.1).
优选地，所述三羟甲基丙烷脂肪酸酯包括三羟甲基丙烷三油酸酯、三羟甲基丙烷三硬脂酸酯和三羟甲基丙烷三异硬脂酸酯中的一种或几种。Preferably, the trimethylolpropane fatty acid ester comprises one of trimethylolpropane trioleate, trimethylolpropane tristearate and trimethylolpropane triisostearate or several.
优选地，所述第二加脂活性组分的制备原料中，山梨醇酐酯类化合物、顺丁烯二酸酐和亚硫酸酸源中亚硫酸根的摩尔比为1：(0.8～1)：(0.9～1.1)。Preferably, in the raw materials for the preparation of the second fatliquoring active component, the molar ratio of sulfite in the sorbitan ester compound, maleic anhydride and sulfurous acid source is 1: (0.8-1): (0.9～1.1).
优选地，所述第一加脂活性组分和第二加脂活性组分的制备原料中的亚硫酸根独立地包括焦亚硫酸盐、亚硫酸氢盐和亚硫酸盐中的一种或几种。Preferably, the sulfite in the preparation raw materials of the first fat-liquor active component and the second fat-liquor active component independently includes one or more of pyrosulfite, bisulfite and sulfite. kind.
优选地，所述第三加脂活性组分中二聚酸与聚乙二醇的摩尔比为1：(0.9～1.1)。Preferably, the molar ratio of dimer acid to polyethylene glycol in the third fat-liquoring active component is 1: (0.9-1.1).
优选地，所述第一加脂活性组分、第二加脂活性组分和第三加脂活性组分的制备原料独立地还包括防霉剂和/或杀菌剂。Preferably, the raw materials for the preparation of the first fat-liquor active component, the second fat-liquor active component and the third fat-liquor active component independently further include an antifungal agent and/or a fungicide.
优选地，所述乳化剂包括聚氧乙烯醚类化合物、聚氧乙烯醚酯类化合物、聚氧乙烯醚盐类化合物、酸酯盐类化合物和葡糖苷类化合物中的一种或几种。Preferably, the emulsifier includes one or more of polyoxyethylene ether compounds, polyoxyethylene ether ester compounds, polyoxyethylene ether salt compounds, ester salt compounds and glucoside compounds.
本发明提供了上述技术方案所述合成加脂剂的制备方法，包括以下步骤：The present invention provides the preparation method of the synthetic fatliquor described in above-mentioned technical scheme, comprises the following steps:
(1)将三羟甲基丙烷脂肪酸酯和乙醇胺混合进行酯交换-酰胺反应，得到三羟甲基丙烷脂肪酸酰胺反应液；(1) trimethylolpropane fatty acid ester and ethanolamine are mixed to carry out transesterification-amide reaction, obtain trimethylolpropane fatty acid amide reaction liquid;
将所述三羟甲基丙烷脂肪酸酰胺反应液和顺丁烯二酸酐混合，进行酯化反应，得到三羟甲基丙烷脂肪酸-马来酸单酯反应液；The trimethylolpropane fatty acid amide reaction solution is mixed with maleic anhydride to perform an esterification reaction to obtain a trimethylolpropane fatty acid-maleic acid monoester reaction solution;
利用pH调节剂将所述三羟甲基丙烷脂肪酸-马来酸单酯反应液的pH值至6.5～7.5后与亚硫酸根混合，进行亚硫酸化反应，得到第一加脂活性组分；Using a pH regulator to adjust the pH value of the trimethylolpropane fatty acid-maleic acid monoester reaction liquid to 6.5-7.5, mix it with sulfite, and carry out sulfitation reaction to obtain the first fatliquoring active component;
(2)将山梨醇酐酯类化合物与顺丁烯二酸酐混合，进行酯化反应，得到马来酸单山梨醇酐酯反应液；(2) mix sorbitan ester compound with maleic anhydride, carry out esterification reaction, obtain maleic acid monosorbitan ester reaction liquid;
利用pH调节剂将所述马来酸单山梨醇酐酯反应液的pH值至5～5.5后与亚硫酸根混合，进行亚硫酸化反应，得到第二加脂活性组分；Using a pH regulator to adjust the pH value of the maleic acid monosorbitan ester reaction solution to 5-5.5, mix it with sulfite, and perform a sulfitation reaction to obtain a second fatliquoring active component;
(3)将二聚酸与聚乙二醇混合，进行酯化反应，得到第三加脂活性组分；(3) mixing the dimer acid and polyethylene glycol to carry out esterification reaction to obtain the third fatliquoring active component;
(4)将所述第一加脂活性组分、所述第二加脂活性组分、所述第三加脂活性组分与乳化剂、助溶剂以及水混合，得到合成加脂剂；当所述乳化剂、助溶剂和水中的一种或几种的质量份数为0时，省略质量份数为0的制备原料；(4) mixing the first fat-liquor active component, the second fat-liquor active component, and the third fat-liquor active component with an emulsifier, a cosolvent, and water to obtain a synthetic fat-liquor; When the mass fraction of one or more of the emulsifier, co-solvent and water is 0, omit the preparation raw material whose mass fraction is 0;
步骤(1)～(3)没有时间先后顺序。Steps (1) to (3) are not in chronological order.
本发明还提供了上述技术方案所述合成加脂剂或上述技术方案所述制备方法制备得到的合成加脂剂在皮革中的应用。The present invention also provides the application of the synthetic fatliquoring agent described in the above technical scheme or the synthetic fatliquoring agent prepared by the preparation method described in the above technical scheme in leather.
本发明提供了一种合成加脂剂，包括以下质量份数的制备原料：第一加脂活性组分15～50份，第二加脂活性组分5～25份，第三加脂活性组分5～25份，乳化剂0～15份，助溶剂0～15份和水0～200份；所述第一加脂活性组分的制备原料包括三羟甲基丙烷脂肪酸酯、乙醇胺、顺丁烯二酸酐、pH调节剂和亚硫酸根；所述第二加脂活性组分的制备原料包括山梨醇酐酯类化合物、顺丁烯二酸酐、pH调节剂和亚硫酸根；所述第三加脂活性组分的制备原料为二聚酸和聚乙二醇的酯化产物。在本发明中，第一加脂组分含有羟基、羧基及磺酸基，与皮革胶原纤维有良好的结合力，第二加脂组分含有的山梨醇有良好的保湿作用，赋予皮革良好的滋润感，第三加脂组分的聚乙二醇同样具有良好的保湿作用，二聚酸比常规脂肪酸有更佳的油润感，充分润滑皮革胶原纤维，赋予皮革良好的柔软度。本发明提供的合成加脂剂中含有氨基、羟基、羧基和磺酸基等多种活性官能团，与皮革胶原纤维的结合力强，……，提高皮革的柔软度、抗撕力以及皮革对于的合成加脂剂吸收率。乳化剂和助溶剂能够进一步提高合成加脂剂的稳定性以及乳化程度，提高皮革的柔软度、抗撕力以及皮革对于的合成加脂剂吸收率。助溶剂和水能够降低合成加脂剂的粘度，降低生产成本。如实施例测试结果所示，本发明提供的合成加脂剂后的处理皮革的柔软度在7.796以上，表面手感油润，抗撕力在66.91N以上，吸收率在90％以上，说明，本发明提供的合成加脂剂能够提高皮革的柔软度、抗撕力和对合成加脂剂的吸收率。The invention provides a synthetic fatliquoring agent, which comprises the following preparation raw materials in parts by mass: 15-50 parts of the first fatliquoring active component, 5-25 parts of the second fatliquoring active component, 5-25 parts of the third fatliquoring active component 5 to 25 parts, 0 to 15 parts of emulsifier, 0 to 15 parts of cosolvent and 0 to 200 parts of water; the raw materials for the preparation of the first fatliquoring active component include trimethylolpropane fatty acid ester, ethanolamine, Maleic anhydride, pH regulator and sulfite; the raw materials for the preparation of the second fatliquoring active component include sorbitan ester compounds, maleic anhydride, pH regulator and sulfite; the The raw material for the preparation of the third fatliquoring active component is the esterification product of dimer acid and polyethylene glycol. In the present invention, the first fatliquoring component contains hydroxyl group, carboxyl group and sulfonic acid group, and has good binding force with leather collagen fiber; Moisturizing, polyethylene glycol in the third fatliquoring component also has a good moisturizing effect, dimer acid has a better oily feel than conventional fatty acids, fully lubricates leather collagen fibers, and gives leather good softness. The synthetic fatliquoring agent provided by the present invention contains various active functional groups such as amino, hydroxyl, carboxyl and sulfonic acid groups, and has a strong binding force with leather collagen fibers, and improves the softness, tear resistance and durability of leather Absorption rate of synthetic fatliquor. Emulsifiers and co-solvents can further improve the stability and emulsification degree of synthetic fatliquors, and improve the softness, tear resistance and absorption rate of synthetic fatliquors for leather. Co-solvents and water reduce the viscosity of synthetic fatliquors and reduce production costs. As shown in the test results of the examples, the softness of the treated leather after the synthetic fatliquoring agent provided by the present invention is above 7.796, the surface feels oily, the tear resistance is above 66.91N, and the absorption rate is above 90%. The synthetic fatliquoring agent provided by the invention can improve the softness, tear resistance and absorption rate of the synthetic fatliquoring agent of leather.
本发明提供了上述技术方案所述合成加脂剂的制备方法。本发明提供的制备方法操作简单，制备原料廉价易得，生产成本低，适宜工业化生产。The invention provides a method for preparing the synthetic fatliquoring agent described in the above technical scheme. The preparation method provided by the invention is simple to operate, the preparation raw materials are cheap and easy to obtain, the production cost is low, and it is suitable for industrial production.
本发明提供的合成加脂剂应用于皮革中时，不产生三废，绿色环保。When the synthetic fatliquoring agent provided by the invention is applied to leather, it does not produce three wastes and is environmentally friendly.
具体实施方式Detailed ways
本发明提供了一种合成加脂剂，包括以下质量份数的制备原料：第一加脂活性组分15～50份，第二加脂活性组分5～25份，第三加脂活性组分5～25份，乳化剂0～15份，助溶剂0～15份和水0～200份；The invention provides a synthetic fatliquoring agent, which comprises the following preparation raw materials in parts by mass: 15-50 parts of the first fatliquoring active component, 5-25 parts of the second fatliquoring active component, 5-25 parts of the third fatliquoring active component 5 to 25 parts, 0 to 15 parts of emulsifier, 0 to 15 parts of cosolvent and 0 to 200 parts of water;
所述第一加脂活性组分的制备原料包括三羟甲基丙烷脂肪酸酯、乙醇胺、顺丁烯二酸酐、pH调节剂和亚硫酸根；The raw materials for the preparation of the first fatliquoring active component include trimethylolpropane fatty acid ester, ethanolamine, maleic anhydride, pH regulator and sulfite;
所述第二加脂活性组分的制备原料包括山梨醇酐酯类化合物、顺丁烯二酸酐、pH调节剂和亚硫酸根；The raw materials for the preparation of the second fatliquoring active component include sorbitan ester compounds, maleic anhydride, pH regulator and sulfite;
所述第三加脂活性组分为二聚酸和聚乙二醇的酯化产物。The third fatliquoring active component is the esterification product of dimer acid and polyethylene glycol.
在本发明中，若无特殊说明，所有的原料组分均为本领域技术人员熟知的市售商品。In the present invention, unless otherwise specified, all raw material components are commercially available products well known to those skilled in the art.
以质量份数计，本发明提供的合成加脂剂的制备原料包括第一加脂活性组分15～50份，优选为20～45份，更优选为25～40份，进一步优选为30～35份。在本发明中，所述第一加脂活性组分的制备原料优选包括三羟甲基丙烷脂肪酸酯、乙醇胺、顺丁烯二酸酐、pH调节剂和亚硫酸根。在本发明中，所述三羟甲基丙烷脂肪酸酯优选包括三羟甲基丙烷三油酸酯、三羟甲基丙烷三硬脂酸酯和三羟甲基丙烷三异硬脂酸酯中的一种或几种。本发明采用的三羟甲基丙烷脂肪酸酯中羟基含量多，能够提高合成加脂剂的亲水性和保湿性。在本发明中，所述亚硫酸根优选由亚硫酸根源提供，所述亚硫酸根源优选包括焦亚硫酸盐、亚硫酸氢盐和亚硫酸盐中的一种或几种，更优选包括焦亚硫酸钠、焦亚硫酸钾、亚硫酸氢钠、亚硫酸氢钾、亚硫酸钠和亚硫酸钠钾中的一种或几种；所述亚硫酸根优选以亚硫酸根水溶液形式使用，所述亚硫酸根水溶液的浓度优选为15～40wt％，更优选为25wt％。在本发明中，所述pH调节剂优选包括无机碱和/或有机碱，所述无机碱优选包括氢氧化钠、氢氧化钾和氨水中的一种或几种；所述有机碱优选包括一乙醇胺、二乙醇胺和三乙醇胺中的一种或几种；所述pH调节剂优选以pH调节剂水溶液形式使用，所述所述pH调节剂水溶液的浓度优选为20～50wt％，更优选为30～40wt％。在本发明中，所述三羟甲基丙烷脂肪酸酯、乙醇胺、顺丁烯二酸酐、亚硫酸酸源中亚硫酸根摩尔比优选优选为1：(0.9～1.1)：(0.9～1.1)：(0.9～1.1)，更优选为1：(0.95～1.05)：(0.95～1.05)：(0.95～1.05)，进一步优选为1:1:1:1。在本发明中，所述第一加脂活性组分的制备原料优选还包括防霉剂和/或杀菌剂；所述防霉剂的质量优选为三羟甲基丙烷脂肪酸酯质量的0～2％，更优选为0.1～0.4％；所述杀菌剂的质量优选为三羟甲基丙烷脂肪酸酯质量的0～2％，更优选为0.1～0.4％；本发明对于所述防霉剂和杀菌剂的种类没有特殊限定，采用本领域技术人员熟知的防霉剂和杀菌剂即可，在本发明的具体实施例中，所述防霉剂优选为吡啶硫酮锌；所述杀菌剂优选为卡松。In terms of parts by mass, the raw materials for the preparation of the synthetic fatliquor provided by the present invention include 15-50 parts of the first fatliquoring active component, preferably 20-45 parts, more preferably 25-40 parts, and even more preferably 30-40 parts. 35 servings. In the present invention, the raw materials for the preparation of the first fatliquoring active component preferably include trimethylolpropane fatty acid ester, ethanolamine, maleic anhydride, pH regulator and sulfite. In the present invention, the trimethylolpropane fatty acid ester preferably includes trimethylolpropane trioleate, trimethylolpropane tristearate and trimethylolpropane triisostearate one or more of. The trimethylolpropane fatty acid ester adopted in the invention has a large hydroxyl content, which can improve the hydrophilicity and moisture retention of the synthetic fatliquoring agent. In the present invention, the sulfite is preferably provided by a sulfite source, and the sulfite source preferably includes one or more of pyrosulfite, bisulfite and sulfite, more preferably sodium pyrosulfite , potassium pyrosulfite, sodium bisulfite, potassium bisulfite, sodium sulfite and potassium sodium sulfite; the sulfite is preferably used in the form of aqueous sulfite solution, and the concentration of the aqueous solution of sulfite Preferably it is 15 to 40 wt%, more preferably 25 wt%. In the present invention, the pH regulator preferably includes an inorganic base and/or an organic base, and the inorganic base preferably includes one or more of sodium hydroxide, potassium hydroxide and ammonia; the organic base preferably includes a One or more of ethanolamine, diethanolamine and triethanolamine; the pH regulator is preferably used in the form of an aqueous solution of the pH regulator, and the concentration of the aqueous solution of the pH regulator is preferably 20 to 50 wt%, more preferably 30 ~40wt%. In the present invention, the molar ratio of sulfite in the trimethylolpropane fatty acid ester, ethanolamine, maleic anhydride, and sulfurous acid source is preferably 1: (0.9-1.1): (0.9-1.1) : (0.9-1.1), more preferably 1: (0.95-1.05): (0.95-1.05): (0.95-1.05), more preferably 1:1:1:1. In the present invention, the raw materials for the preparation of the first fatliquoring active component preferably further include an antifungal agent and/or a bactericide; 2%, more preferably 0.1 to 0.4%; the quality of the fungicide is preferably 0 to 2% of the trimethylolpropane fatty acid ester quality, more preferably 0.1 to 0.4%; the present invention is for the fungicide And the kind of bactericide is not particularly limited, adopts antifungal agent and bactericide well known to those skilled in the art, and in a specific embodiment of the present invention, said antifungal agent is preferably zinc pyrithione; said bactericide Casson is preferred.
以所述第一加脂活性组分的质量份数计，所述本发明提供的合成加脂剂的制备原料包括第二加脂活性组分5～25份，优选为10～20份，进一步优选为15～20份。在本发明中，所述第二加脂活性组分的制备原料包括山梨醇酐酯类化合物、顺丁烯二酸酐、pH调节剂和亚硫酸根；所述山梨醇酐酯类化合物优选包括司盘类化合物和吐温类化合物中的一种或几种；所述司盘类化合物优选包括司盘65(山梨醇酐三硬脂酸酯)和/或司盘85(山梨醇酐三油酸酯)；所述吐温类化合物优选包括吐温65(聚氧乙烯(20)山梨醇酐三硬脂酸酯)和/或吐温85(聚氧乙烯(20)山梨醇酐三油酸酯)；当所述山梨醇酐酯类化合物为司盘类化合物和吐温类化合物的混合物时，所述司盘类化合物和吐温类化合物的质量比优选为12：(12～30)，更优选为12：(20～25)，进一步优选为12:23。在本发明中，所述山梨醇酐酯类化合物、顺丁烯二酸酐和亚硫酸酸源中亚硫酸根的摩尔比优选为1：(0.8～1)：(0.9～1.1)，更优选为1：(0.85～95)：(0.95～1.05)，更优选为1:0.9:1。在本发明中，所述第二加脂活性组分的制备原料优选还包括防霉剂和/或杀菌剂；所述防霉剂的质量优选为三山梨醇酐酯类化合物质量的0～2％，更优选为0.1～0.4％；所述杀菌剂的质量优选为山梨醇酐酯类化合物质量的0～2％，更优选为0.1～0.4％。在本发明中，所述第二加脂活性组分地制备原料中的pH调节剂、亚硫酸根源、防霉剂和杀菌剂的可选种类优选与所述第一加脂活性组分的制备原料中的pH调节剂、亚硫酸根源、防霉剂和杀菌剂的可选种类相同，在此不再一一赘述。In terms of the number of parts by mass of the first fatliquoring active component, the raw materials for the preparation of the synthetic fatliquoring agent provided by the present invention include 5 to 25 parts, preferably 10 to 20 parts, of the second fatliquoring active component, further Preferably it is 15 to 20 parts. In the present invention, the raw materials for the preparation of the second fatliquoring active component include sorbitan ester compounds, maleic anhydride, pH regulators and sulfite; the sorbitan ester compounds preferably include One or more of Span compounds and Tween compounds; said Span compounds preferably include Span 65 (Sorbitan tristearate) and/or Span 85 (Sorbitan trioleate ester); the Tween compounds preferably include Tween 65 (polyoxyethylene (20) sorbitan tristearate) and/or Tween 85 (polyoxyethylene (20) sorbitan trioleate ); when the sorbitan ester compound is a mixture of Span compounds and Tween compounds, the mass ratio of the Span compounds and Tween compounds is preferably 12: (12～30), more Preferably it is 12:(20-25), and it is more preferable that it is 12:23. In the present invention, the molar ratio of sulfite in the sorbitan ester compound, maleic anhydride and sulfurous acid source is preferably 1:(0.8～1):(0.9～1.1), more preferably 1:(0.85-95):(0.95-1.05), more preferably 1:0.9:1. In the present invention, the raw materials for the preparation of the second fatliquoring active component preferably also include antifungal agents and/or bactericides; %, more preferably 0.1-0.4%; the mass of the fungicide is preferably 0-2% of the mass of the sorbitan ester compound, more preferably 0.1-0.4%. In the present invention, the optional types of pH regulators, sulfite sources, anti-fungal agents and bactericides in the raw materials for the preparation of the second fat-liquor active component are preferably related to the preparation of the first fat-liquor active component. The optional types of pH regulators, sulfite sources, antifungal agents and bactericides in the raw materials are the same, and will not be repeated here.
以所述第一加脂活性组分的质量份数计，所述本发明提供的合成加脂剂的制备原料包括第三加脂活性组分5～25份，优选为5～20份，更优选为10～15份。在本发明中，所述第三加脂活性组分为二聚酸和聚乙二醇的酯化产物。在本发明中，所述第三加脂活性组分的制备原料优选包括二聚酸、聚乙二醇、酸性催化剂和pH调节剂。在本发明中，所述二聚酸优选为油酸的二聚酸。在本发明中，所述聚乙二醇的分子量优选为200～2000，更优选为400～1000。在本发明中，所述酸性催化剂优选包括对甲苯磺酸、浓硫酸和固体酸中的一种或几种。在本发明中，所述浓硫酸的浓度优选≥98wt％。在本发明中，所述固体酸优选包括固载化液体酸、酸性氧化物、过渡金属硫化物、磷酸盐、硫酸盐、沸石分子筛、杂多酸、阳离子交换树脂、天然黏土矿和固体超强酸中的一种或几种。在本发明中，所述固载化液体酸优选包括HF/Al2O3、BF3/Al2O3和H3PO4/硅藻土中的一种或几种。在本发明中，所述酸性氧化物优选包括Al2O3、SiO2、B2O3、Nb2O5、Al2O3-SiO2和Al2O3-B2O3中的一种或几种。在本发明中，所述过渡金属硫化物优选包括CdS和ZnS中的一种或两种。在本发明中，所述磷酸盐优选包括AlPO4和BPO4中的一种或两种。在本发明中，所述硫酸盐优选包括Fe2(SO4)3、Al2(SO4)3和CuSO4中的一种或几种。在本发明中，所述沸石分子筛优选包括ZSM-5沸石、X沸石、Y沸石、B沸石、丝光沸石和AIRO SAPO分子筛中的一种或几种。在本发明中，所述杂多酸优选包括H3PW12O40、H4SiW12O40和H3PMo12O40中的一种或几种。在本发明中，所述阳离子交换树脂优选包括苯乙烯-二乙烯基苯共聚物和Nafion-H中的一种或两种。在本发明中，所述天然黏土矿优选包括高岭土、膨润土和蒙脱土中的一种或几种。在本发明中，所述固体超强酸优选包括SO4 2-/ZrO2、WO3/ZrO2、MoO3/ZrO2和B2O3/ZrO2中的一种或几种。在本发明中，所述酸性催化剂的质量优选为二聚酸质量的0.5～2％，更优选为0.5～1.5％，进一步优选为1～1.5％。在本发明中，所述第三加脂活性组分的制备原料优选还包括防霉剂和/或杀菌剂；所述防霉剂的质量优选为二聚酸质量的0～2％，更优选为0.1～1％，进一步优选为0.1～0.4％；所述杀菌剂的质量优选为二聚酸质量的0～2％，更优选为0.1～1％，进一步优选为0.1～0.4％。在本发明中，所述第三加脂活性组分地制备原料中的pH调节剂、防霉剂和杀菌剂的可选种类优选与所述第一加脂活性组分的制备原料中的pH调节剂、防霉剂和杀菌剂的可选种类相同，在此不再一一赘述。In terms of the number of parts by mass of the first fatliquoring active component, the raw materials for the preparation of the synthetic fatliquoring agent provided by the present invention include 5-25 parts, preferably 5-20 parts, of the third fatliquoring active component, more preferably Preferably it is 10 to 15 parts. In the present invention, the third fatliquoring active component is the esterification product of dimer acid and polyethylene glycol. In the present invention, the raw materials for the preparation of the third fatliquoring active component preferably include dimer acid, polyethylene glycol, acidic catalyst and pH regulator. In the present invention, the dimer acid is preferably a dimer acid of oleic acid. In the present invention, the molecular weight of the polyethylene glycol is preferably 200-2000, more preferably 400-1000. In the present invention, the acid catalyst preferably includes one or more of p-toluenesulfonic acid, concentrated sulfuric acid and solid acid. In the present invention, the concentration of the concentrated sulfuric acid is preferably ≥98wt%. In the present invention, the solid acid preferably includes immobilized liquid acid, acid oxide, transition metal sulfide, phosphate, sulfate, zeolite molecular sieve, heteropolyacid, cation exchange resin, natural clay mineral and solid superacid one or more of them. In the present invention, the immobilized liquid acid preferably includes one or more of HF/Al 2 O 3 , BF 3 /Al 2 O 3 and H 3 PO 4 /diatomaceous earth. In the present invention, the acidic oxide preferably includes one of Al 2 O 3 , SiO 2 , B 2 O 3 , Nb 2 O 5 , Al 2 O 3 -SiO 2 and Al 2 O 3 -B 2 O 3 species or several. In the present invention, the transition metal sulfide preferably includes one or both of CdS and ZnS. In the present invention, the phosphate preferably includes one or both of AlPO 4 and BPO 4 . In the present invention, the sulfate preferably includes one or more of Fe 2 (SO 4 ) 3 , Al 2 (SO 4 ) 3 and CuSO 4 . In the present invention, the zeolite molecular sieve preferably includes one or more of ZSM-5 zeolite, X zeolite, Y zeolite, B zeolite, mordenite and AIRO SAPO molecular sieve. In the present invention, the heteropoly acid preferably includes one or more of H 3 PW 12 O 40 , H 4 SiW 12 O 40 and H 3 PMo 12 O 40 . In the present invention, the cation exchange resin preferably includes one or both of styrene-divinylbenzene copolymer and Nafion-H. In the present invention, the natural clay ore preferably includes one or more of kaolin, bentonite and montmorillonite. In the present invention, the solid superacid preferably includes one or more of SO 4 2− /ZrO 2 , WO 3 /ZrO 2 , MoO 3 /ZrO 2 and B 2 O 3 /ZrO 2 . In the present invention, the mass of the acidic catalyst is preferably 0.5-2% of the mass of the dimer acid, more preferably 0.5-1.5%, even more preferably 1-1.5%. In the present invention, the raw material for the preparation of the third fatliquoring active component preferably further includes an antifungal agent and/or a fungicide; the mass of the antifungal agent is preferably 0-2% of the mass of the dimer acid, more preferably 0.1-1%, more preferably 0.1-0.4%; the mass of the bactericide is preferably 0-2% of the mass of the dimer acid, more preferably 0.1-1%, even more preferably 0.1-0.4%. In the present invention, the optional types of pH regulators, anti-fungal agents and bactericides in the preparation raw materials of the third fat-liquor active component are preferably the same as the pH in the preparation raw materials of the first fat-liquor active component. The optional types of regulators, anti-fungal agents and bactericides are the same, and will not be repeated here.
以所述第一加脂活性组分的质量份数计，所述本发明提供的合成加脂剂的制备原料包括乳化剂0～15份，优选为1～15份，更优选为3～12份，进一步优选为5～10份。在本发明中，所述乳化剂包括聚氧乙烯醚类化合物、聚氧乙烯醚酯类化合物、聚氧乙烯醚盐类化合物、酸酯盐类化合物和葡糖苷类化合物中的一种或几种；所述聚氧乙烯醚类化合物优选包括脂肪醇聚氧乙烯醚和脂肪酸甲酯聚氧乙烯醚中的至少一种，所述聚氧乙烯醚酯类化合物优选包括脂肪醇聚氧乙烯醚磷酸酯和异辛醇聚氧乙烯醚磷酸酯中的至少一种；所述聚氧乙烯醚盐类化合物优选包括脂肪醇聚氧乙烯醚琥珀酸单酯磺酸盐和脂肪醇聚氧乙烯醚羧酸盐中的至少一种；所述酸酯盐类化合物优选包括烷基马来酸单酯盐和脂肪酸甲酯乙氧基化物磺酸盐中的至少一种；所述葡糖苷类化合物优选包括辛癸基葡糖苷和月桂基葡糖苷中的至少一种。在本发明中，乳化剂的加入能够提高合成加脂剂的乳化性，进而提高其稳定性。In terms of the number of parts by mass of the first fatliquoring active component, the raw materials for the preparation of the synthetic fatliquoring agent provided by the present invention include 0-15 parts of emulsifier, preferably 1-15 parts, more preferably 3-12 parts parts, more preferably 5 to 10 parts. In the present invention, the emulsifier includes one or more of polyoxyethylene ether compounds, polyoxyethylene ether ester compounds, polyoxyethylene ether salt compounds, ester salt compounds and glucoside compounds The polyoxyethylene ether compound preferably includes at least one of fatty alcohol polyoxyethylene ether and fatty acid methyl ester polyoxyethylene ether, and the polyoxyethylene ether ester compound preferably includes fatty alcohol polyoxyethylene ether phosphate and at least one of isooctyl alcohol polyoxyethylene ether phosphate; the polyoxyethylene ether salt compound preferably includes fatty alcohol polyoxyethylene ether succinic acid monoester sulfonate and fatty alcohol polyoxyethylene ether carboxylate at least one of; the ester salt compound preferably includes at least one of alkyl maleic acid monoester salt and fatty acid methyl ester ethoxylate sulfonate; the glucoside compound preferably includes octadecylglucose At least one of glycoside and lauryl glucoside. In the present invention, adding the emulsifier can improve the emulsifying property of the synthetic fatliquoring agent, and further improve its stability.
以所述第一加脂活性组分的质量份数计，所述本发明提供的合成加脂剂的制备原料包括助溶剂0～15份，优选为1～15份，更优选为3～12份，进一步优选为5～10份。在本发明中，所述助溶剂优选包括醇类溶剂和/或醚类溶剂；所述醇类溶剂优选包括乙醇、异丙醇、乙二醇、1,2-丙二醇、1,3丙二醇、2-甲基-2,4-戊二醇、异己二醇和聚乙二醇中的至少一种；所述醚类溶剂优选包括乙二醇丁醚和/或乙二醇甲醚。在本发明中，助溶剂的加入能够提高合成加脂剂的稳定性以及降低其粘度。In terms of the number of parts by mass of the first fatliquoring active component, the raw materials for the preparation of the synthetic fatliquoring agent provided by the present invention include 0-15 parts of co-solvent, preferably 1-15 parts, more preferably 3-12 parts parts, more preferably 5 to 10 parts. In the present invention, the co-solvent preferably includes alcohol solvents and/or ether solvents; the alcohol solvents preferably include ethanol, isopropanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2 - At least one of methyl-2,4-pentanediol, isohexanediol and polyethylene glycol; the ether solvent preferably includes ethylene glycol butyl ether and/or ethylene glycol methyl ether. In the present invention, the addition of co-solvent can improve the stability of the synthetic fatliquoring agent and reduce its viscosity.
以所述第一加脂活性组分的质量份数计，所述本发明提供的合成加脂剂的制备原料包括水0～200份，优选为20～200份，更优选为30～150份。在本发明中，助溶剂的加入能够提高合成加脂剂的稳定性以及降低其粘度。In terms of the number of parts by mass of the first fatliquoring active component, the raw materials for the preparation of the synthetic fatliquoring agent provided by the present invention include 0-200 parts of water, preferably 20-200 parts, more preferably 30-150 parts . In the present invention, the addition of co-solvent can improve the stability of the synthetic fatliquoring agent and reduce its viscosity.
本发明提供了上述技术方案所述合成加脂剂的制备方法，包括以下步骤：The present invention provides the preparation method of the synthetic fatliquor described in above-mentioned technical scheme, comprises the following steps:
(1)将三羟甲基丙烷脂肪酸酯和乙醇胺混合进行酯交换-酰胺反应，得到三羟甲基丙烷脂肪酸酰胺反应液；(1) trimethylolpropane fatty acid ester and ethanolamine are mixed to carry out transesterification-amide reaction, obtain trimethylolpropane fatty acid amide reaction liquid;
将所述三羟甲基丙烷脂肪酸酰胺反应液和顺丁烯二酸酐混合，进行酯化反应，得到三羟甲基丙烷脂肪酸-马来酸单酯反应液；The trimethylolpropane fatty acid amide reaction solution is mixed with maleic anhydride to perform an esterification reaction to obtain a trimethylolpropane fatty acid-maleic acid monoester reaction solution;
利用pH调节剂将所述三羟甲基丙烷脂肪酸-马来酸单酯反应液的pH值至6.5～7.5后与亚硫酸根混合，进行亚硫酸化反应，得到第一加脂活性组分；Using a pH regulator to adjust the pH value of the trimethylolpropane fatty acid-maleic acid monoester reaction liquid to 6.5-7.5, mix it with sulfite, and carry out sulfitation reaction to obtain the first fatliquoring active component;
(2)将山梨醇酐酯类化合物与顺丁烯二酸酐混合，进行酯化反应，得到马来酸单山梨醇酐酯反应液；(2) mix sorbitan ester compound with maleic anhydride, carry out esterification reaction, obtain maleic acid monosorbitan ester reaction solution;
利用pH调节剂将所述马来酸单山梨醇酐酯反应液的pH值至5～5.5后与亚硫酸根混合，进行亚硫酸化反应，得到第二加脂活性组分；Using a pH regulator to adjust the pH value of the maleic acid monosorbitan ester reaction solution to 5-5.5, mix it with sulfite, and perform a sulfitation reaction to obtain a second fatliquoring active component;
(3)将二聚酸与聚乙二醇，进行酯化反应，得到第三加脂活性组分；(3) carrying out esterification reaction with dimer acid and polyethylene glycol to obtain the third fatliquoring active component;
(4)将所述第一加脂活性组分、所述第二加脂活性组分、所述第三加脂活性组分与乳化剂、助溶剂以及水混合，得到合成加脂剂；当所述乳化剂、助溶剂和水中的一种或几种的质量份数为0时，省略质量份数为0的制备原料；(4) mixing the first fat-liquor active component, the second fat-liquor active component, and the third fat-liquor active component with an emulsifier, a cosolvent, and water to obtain a synthetic fat-liquor; When the mass fraction of one or more of the emulsifier, co-solvent and water is 0, omit the preparation raw material whose mass fraction is 0;
步骤(1)～(3)没有时间先后顺序。Steps (1) to (3) are not in chronological order.
本发明将三羟甲基丙烷脂肪酸酯和乙醇胺混合进行酯交换-酰胺反应，得到三羟甲基丙烷脂肪酸酰胺反应液。在本发明中，所述混合优选为搅拌混合，本发明对于所述搅拌混合的转速没有特殊限定，能够将原料混合均匀即可。在本发明的具体实施例中，所述混合优选为：将三羟甲基丙烷脂肪酸酯的温度升至60～120℃(更优选为80～100℃)，抽真空至三羟甲基丙烷脂肪酸酯的含水率在0.1wt％以下，加入乙醇胺混合。在本发明中，所述酯交换-酰胺反应的温度优选为100～200℃，更优选为140～160℃，所述酯交换-酰胺反应的时间优选为3～5h，更优选为4h。The invention mixes trimethylolpropane fatty acid ester and ethanolamine to carry out transesterification-amide reaction to obtain trimethylolpropane fatty acid amide reaction liquid. In the present invention, the mixing is preferably stirring and mixing, and the present invention has no special limitation on the rotational speed of the stirring and mixing, as long as the raw materials can be mixed evenly. In a specific embodiment of the present invention, the mixing is preferably: raising the temperature of the trimethylolpropane fatty acid ester to 60-120° C. (more preferably 80-100° C.), and vacuuming the trimethylolpropane to The water content of the fatty acid ester is below 0.1wt%, adding ethanolamine and mixing. In the present invention, the temperature of the transesterification-amide reaction is preferably 100-200°C, more preferably 140-160°C, and the time of the transesterification-amide reaction is preferably 3-5h, more preferably 4h.
得到三羟甲基丙烷脂肪酸酰胺反应液后，本发明将所述三羟甲基丙烷脂肪酸酰胺反应液和顺丁烯二酸酐混合，进行酯化反应，得到三羟甲基丙烷脂肪酸-马来酸单酯反应液。在本发明中，所述混合优选为搅拌混合，本发明对于所述搅拌混合的转速没有特殊限定，能够将原料混合均匀即可。在本发明的具体实施例中，所述混合优选为：将所述三羟甲基丙烷脂肪酸酰胺反应液的温度降低至100～200℃(更优选为120～150℃)，抽真空30～60min(更优选为40～50min)，之后降温至90～100℃(更优选为95～100℃)；所述混合的温度过高会导致反应体系的颜色加深，影响亲水保湿性能。在本发明中，所述酯化反应优选包括依次进行第一酯化反应和第二酯化反应，所述第一酯化反应的温度优选为90～100℃，更优选为95～100℃；所述第一酯化反应的时间优选为2～3h，更优选为2.5h；所述第二酯化反应的温度优选为110～150℃，更优选为120～140℃；所述第二酯化反应的时间优选为30～120min，更优选为50～100min。After the trimethylolpropane fatty acid amide reaction solution is obtained, the present invention mixes the trimethylolpropane fatty acid amide reaction solution with maleic anhydride for esterification to obtain trimethylolpropane fatty acid-maleic acid mono Ester reaction solution. In the present invention, the mixing is preferably stirring and mixing, and the present invention has no special limitation on the rotational speed of the stirring and mixing, as long as the raw materials can be mixed evenly. In a specific embodiment of the present invention, the mixing is preferably: lowering the temperature of the trimethylolpropane fatty acid amide reaction solution to 100-200°C (more preferably 120-150°C), and vacuuming for 30-60min (more preferably 40-50 minutes), and then lower the temperature to 90-100° C. (more preferably 95-100° C.); if the mixing temperature is too high, the color of the reaction system will deepen and affect the hydrophilic and moisturizing properties. In the present invention, the esterification reaction preferably includes performing the first esterification reaction and the second esterification reaction in sequence, and the temperature of the first esterification reaction is preferably 90-100°C, more preferably 95-100°C; The time of the first esterification reaction is preferably 2 to 3 hours, more preferably 2.5 hours; the temperature of the second esterification reaction is preferably 110 to 150°C, more preferably 120 to 140°C; the second esterification The reaction time is preferably 30 to 120 min, more preferably 50 to 100 min.
得到三羟甲基丙烷脂肪酸-马来酸单酯反应液后，本发明利用pH调节剂将所述三羟甲基丙烷脂肪酸-马来酸单酯反应液的pH值至6.5～7.5后与亚硫酸根混合，进行亚硫酸化反应，得到第一加脂活性组分。在本发明中，优选先将所述三羟甲基丙烷脂肪酸-马来酸单酯反应液的温度降低至40～50℃(更优选为45℃)后再调节pH值。本发明对于所述pH调节剂的用量没有特殊限定，能够将pH值调节至6.5～7.5(更优选为7)即可；所述pH调节剂的加入方式优选为滴加，本发明对于所述滴加的速度没有特殊限定，匀速逐滴加入即可；在本发明中，所述pH值过高，会导致焦亚硫酸钠分解。在本发明中，所述亚硫酸化反应的温度优选为70～75℃，更优选为72～73℃；所述亚硫酸化反应的时间优选为30～60min，更优选为40～50min。After obtaining the trimethylolpropane fatty acid-maleic acid monoester reaction solution, the present invention uses a pH regulator to bring the pH value of the trimethylolpropane fatty acid-maleic acid monoester reaction solution to 6.5 to 7.5 and then mix with sub Sulfate radicals are mixed for sulfitation reaction to obtain the first fatliquoring active component. In the present invention, it is preferable to lower the temperature of the trimethylolpropane fatty acid-maleic acid monoester reaction solution to 40-50° C. (more preferably 45° C.) before adjusting the pH value. In the present invention, there is no special limitation on the amount of the pH regulator, and the pH value can be adjusted to 6.5 to 7.5 (more preferably 7); the addition method of the pH regulator is preferably dropwise, and the present invention is for the The dropping speed is not particularly limited, and it is enough to add dropwise at a uniform speed; in the present invention, if the pH value is too high, it will cause the decomposition of sodium metabisulfite. In the present invention, the temperature of the sulfitation reaction is preferably 70-75°C, more preferably 72-73°C; the time of the sulfitation reaction is preferably 30-60min, more preferably 40-50min.
在本发明中，所述第一加脂活性组分的制备过程中发生的反应如下，其中，R包括油酸基、硬脂酸基、月桂酸基或棕榈酸基。In the present invention, the reaction occurring during the preparation of the first fat-liquor active component is as follows, wherein, R includes oleic acid group, stearic acid group, lauric acid group or palmitic acid group.
当所述第一加脂活性组分的制备原料还包括防霉剂和/或杀菌剂时，所述亚硫酸化反应后优选还包括将所得亚硫酸化反应液与防霉剂和/或杀菌剂混合，得到第一加脂活性组分。When the raw materials for the preparation of the first fatliquoring active component also include antifungal agents and/or bactericides, the sulfitation reaction preferably also includes mixing the obtained sulfitation reaction liquid with antifungal agents and/or bactericidal agents. Agents are mixed to obtain the first fat-liquor active component.
本发明将山梨醇酐酯类化合物与顺丁烯二酸酐混合，进行酯化反应，得到马来酸单山梨醇酐酯反应液。在本发明中，所述混合优选为搅拌混合，本发明对于所述搅拌混合的转速没有特殊限定，能够将原料混合均匀即可。在本发明的具体实施例中，所述混合优选为：将山梨醇酐酯类化合物的温度升至60～120℃(更优选为80～100℃)，抽真空至山梨醇酐酯类化合物的含水率在0.1wt％以下，加入顺丁烯二酸酐混合。在本发明中，所述酯化反应的温度优选为120～150℃，更优选为120～140℃，所述酯化反应的时间优选为2～3h，更优选为2.5h。The invention mixes the sorbitan ester compound and the maleic anhydride to carry out esterification reaction to obtain the maleic acid monosorbitan ester reaction liquid. In the present invention, the mixing is preferably stirring and mixing, and the present invention has no special limitation on the rotational speed of the stirring and mixing, as long as the raw materials can be mixed evenly. In a specific embodiment of the present invention, the mixing is preferably: raising the temperature of the sorbitan ester compound to 60-120°C (more preferably 80-100°C), and vacuuming to the temperature of the sorbitan ester compound. When the water content is below 0.1wt%, add maleic anhydride and mix. In the present invention, the temperature of the esterification reaction is preferably 120-150° C., more preferably 120-140° C., and the time of the esterification reaction is preferably 2-3 hours, more preferably 2.5 hours.
得到马来酸单山梨醇酐酯反应液后，本发明利用pH调节剂将所述马来酸单山梨醇酐酯反应液的pH值至5～5.5后与亚硫酸根混合，进行亚硫酸化反应，得到第二加脂活性组分。本发明对于所述pH调节剂的用量没有特殊限定，能够将pH值调节至5～5.5(更优选为7)即可；所述pH调节剂的加入方式优选为滴加，本发明对于所述滴加的速度没有特殊限定，匀速逐滴加入即可。在本发明中，所述亚硫酸化反应的温度优选为70～80℃，更优选为75～78℃；所述亚硫酸化反应的时间优选为60～120min，更优选为80～100min。After obtaining the maleic acid monosorbitan ester reaction solution, the present invention utilizes a pH regulator to adjust the pH value of the maleic acid monosorbitan ester reaction solution to 5 to 5.5 and mix it with sulfite to carry out sulfitation reaction to obtain the second fat-liquor active component. The present invention has no special limitation on the dosage of the pH regulator, it can adjust the pH value to 5-5.5 (more preferably 7); the adding method of the pH regulator is preferably dropwise, the present invention is There is no special limitation on the speed of dropping, and it is sufficient to add dropwise at a uniform speed. In the present invention, the temperature of the sulfitation reaction is preferably 70-80°C, more preferably 75-78°C; the time of the sulfitation reaction is preferably 60-120min, more preferably 80-100min.
当所述第二加脂活性组分的制备原料还包括防霉剂和/或杀菌剂时，所述亚硫酸化反应后优选还包括将所得亚硫酸化反应液与防霉剂和/或杀菌剂混合，得到第二加脂活性组分。When the preparation raw material of the second fatliquoring active component also includes antifungal agent and/or bactericide, after the sulfitation reaction, it preferably also includes mixing the obtained sulfitation reaction liquid with antifungal agent and/or bactericide Agents are mixed to obtain the second fat-liquor active component.
本发明将二聚酸与聚乙二醇，进行酯化反应，得到第三加脂活性组分。在本发明的具体实施例中，所述第三加脂活性组分的制备方法优选包括以下步骤：将二聚酸、聚乙二醇和酸性催化剂混合，进行酯化反应，然后利用pH调节剂调节pH值至6.5～7.5，得到第三加脂活性组分。在本发明中，所述混合优选为搅拌混合，本发明对于所述搅拌混合的转速没有特殊限定，能够将原料混合均匀即可。在本发明的具体实施例中，所述混合优选为：将二聚酸的温度升至40～80℃(更优选为50～60℃)，加入聚乙二醇和酸性催化剂混合。在本发明中，所述酯化反应的温度优选为110～140℃，更优选为120～140℃，所述酯化反应的时间优选为3～6h，更优选为4～5h。本发明对于所述pH调节剂的用量没有特殊限定，能够将pH值调节至6.5～7.5(更优选为7)即可；所述pH调节剂的加入方式优选为滴加，本发明对于所述滴加的速度没有特殊限定，匀速逐滴加入即可。In the present invention, dimer acid and polyethylene glycol are subjected to esterification reaction to obtain the third fatliquoring active component. In a specific embodiment of the present invention, the preparation method of the third fatliquoring active component preferably includes the following steps: mixing dimer acid, polyethylene glycol and an acid catalyst, performing an esterification reaction, and then using a pH regulator to adjust When the pH value reaches 6.5-7.5, the third fat-liquor active component is obtained. In the present invention, the mixing is preferably stirring and mixing, and the present invention has no special limitation on the rotational speed of the stirring and mixing, as long as the raw materials can be mixed evenly. In a specific embodiment of the present invention, the mixing is preferably: raising the temperature of the dimer acid to 40-80° C. (more preferably 50-60° C.), adding polyethylene glycol and an acidic catalyst and mixing. In the present invention, the temperature of the esterification reaction is preferably 110-140° C., more preferably 120-140° C., and the time of the esterification reaction is preferably 3-6 hours, more preferably 4-5 hours. In the present invention, there is no special limitation on the amount of the pH regulator, and the pH value can be adjusted to 6.5 to 7.5 (more preferably 7); the addition method of the pH regulator is preferably dropwise, and the present invention is for the There is no special limitation on the speed of dropping, and it is sufficient to add dropwise at a uniform speed.
当所述第三加脂活性组分的制备原料还包括防霉剂和/或杀菌剂时，所述亚硫酸化反应后优选还包括将所得亚硫酸化反应液与防霉剂和/或杀菌剂混合，得到第三加脂活性组分。When the preparation raw material of the third fatliquoring active component also includes an antifungal agent and/or a bactericide, after the sulfitation reaction, it preferably also includes mixing the obtained sulfitation reaction liquid with an antifungal agent and/or a bactericide Agents are mixed to obtain the third fat-liquor active component.
得到第一加脂活性组分、第二加脂活性组分和第三加脂活性组分后，本发明将所述第一加脂活性组分、所述第二加脂活性组分、所述第三加脂活性组分与乳化剂、助溶剂以及水混合，得到合成加脂剂；当所述乳化剂、助溶剂和水中的一种或几种的质量份数为0时，省略质量份数为0的制备原料。在本发明中，所述混合优选为搅拌混合，本发明对于所述搅拌混合的转速没有特殊限定，能够将原料混合均匀即可。在本发明的具体实施例中，所述混合优选为：将所述第一加脂活性组分、所述第二加脂活性组分和所述第三加脂活性组分加热至50～90℃混合(更优选为60～80℃)，加入乳化剂和助溶剂混合30～90min(更优选为40～80min)，之后加入水在50～60℃(更优选为55℃)条件下混合。After obtaining the first fat-liquor active component, the second fat-liquor active component and the third fat-liquor active component, the present invention mixes the first fat-liquor active component, the second fat-liquor active component, the The third fatliquoring active component is mixed with an emulsifier, a cosolvent and water to obtain a synthetic fatliquoring agent; when the mass fraction of one or more of the emulsifier, cosolvent and water is 0, the mass Preparation ingredients with 0 parts. In the present invention, the mixing is preferably stirring and mixing, and the present invention has no special limitation on the rotational speed of the stirring and mixing, as long as the raw materials can be mixed evenly. In a specific embodiment of the present invention, the mixing is preferably: heating the first fat-liquor active component, the second fat-liquor active component and the third fat-liquor active component to 50-90°C °C mixing (more preferably 60-80 °C), adding emulsifier and co-solvent and mixing for 30-90 min (more preferably 40-80 min), then adding water and mixing at 50-60 °C (more preferably 55 °C).
本发明还提供了上述技术方案所述合成加脂剂或上述技术方案所述制备方法制备得到的合成加脂剂在皮革中的应用。在本发明中，所述应用优选为合成加脂剂作为加脂剂应用。在本发明中，所述合成加脂剂可以单独使用，也可以与其他加脂剂复配使用。The present invention also provides the application of the synthetic fatliquoring agent described in the above technical scheme or the synthetic fatliquoring agent prepared by the preparation method described in the above technical scheme in leather. In the present invention, the application is preferably the application of a synthetic fatliquoring agent as a fatliquoring agent. In the present invention, the synthetic fatliquor can be used alone or in combination with other fatliquors.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
(1)将三羟甲基丙烷三油酸酯1000g加入到反应设备中，升温至80℃后抽真空至三羟甲基丙烷脂肪酸酯的含水率低于0.1wt％，然后加入乙醇胺60g，继续升温到140℃反应5h，降温至120℃后抽真空60min后降温到100℃，加入顺丁烯二酸酐100g，保温反应2h，再升温到110℃反应30min，降温到50℃，滴加浓度为30wt％的氢氧化钠水溶液调节pH值至6.8，加入浓度为25wt％的焦亚硫酸钠水溶液380g，然后升温至75℃反应60min，降温到室温后加入吡啶硫酮锌1g和卡松1g搅拌均匀，得到第一加脂活性组分。(1) Add 1000 g of trimethylolpropane trioleate into the reaction equipment, heat up to 80° C. and then vacuumize until the water content of trimethylolpropane fatty acid ester is lower than 0.1 wt %, then add 60 g of ethanolamine, Continue to heat up to 140°C for 5 hours, cool down to 120°C and vacuum for 60 minutes, then cool down to 100°C, add 100 g of maleic anhydride, keep warm for 2 hours, then heat up to 110°C for 30 minutes, cool down to 50°C, drop the concentration Adjust the pH value to 6.8 for a 30wt% sodium hydroxide aqueous solution, add 380 g of a 25wt% sodium metabisulfite aqueous solution, then raise the temperature to 75° C. and react for 60 minutes, and then add 1 g of zinc pyrithione and 1 g of Cathone after cooling down to room temperature and stir evenly. A first fat-liquor active ingredient is obtained.
(2)将司盘85480g、吐温85920g加入到反应设备中，升温至80℃后抽真空至原料的含水率低于0.1％，加入顺丁烯二酸酐90g，升温至120℃反应3h，降温到60℃后滴加浓度为30wt％的氢氧化钠水溶液将pH值调节至5.2，加入25wt％的焦亚硫酸钠水溶液360g，然后升温至75℃反应120min，降温到室温后加入加入吡啶硫酮锌2g和卡松2g搅拌均匀，得到第二加脂活性组分。(2) Add Span 85480g and Tween 85920g to the reaction equipment, heat up to 80°C and then evacuate until the moisture content of the raw material is lower than 0.1%, add 90g of maleic anhydride, heat up to 120°C for 3 hours, cool down to After 60°C, add dropwise an aqueous sodium hydroxide solution with a concentration of 30wt% to adjust the pH to 5.2, add 360 g of a 25wt% sodium metabisulfite aqueous solution, then raise the temperature to 75°C and react for 120 minutes, and then add 2 g of zinc pyrithione and Stir 2 g of Kason evenly to obtain the second fatliquoring active component.
(3)将二聚油酸560g加入到反应设备中，升温到50℃，加入聚乙二醇(聚乙二醇与二聚油酸的摩尔比为1:1)，加入对甲苯磺酸7g，升温到120℃反应6h，降温到55℃，滴加浓度为30wt％的氢氧化钠水溶液将pH值调节至6.7，降温到室温后加入吡啶硫酮锌1.2g和卡松1.2g搅拌均匀，得到第三加脂活性组分。(3) Add 560g of dimerized oleic acid to the reaction equipment, raise the temperature to 50°C, add polyethylene glycol (the molar ratio of polyethylene glycol to dimerized oleic acid is 1:1), and add 7g of p-toluenesulfonic acid , the temperature was raised to 120° C. for 6 hours, the temperature was lowered to 55° C., and the pH value was adjusted to 6.7 by adding dropwise an aqueous solution of sodium hydroxide with a concentration of 30 wt %. After cooling down to room temperature, 1.2 g of zinc pyrithione and 1.2 g of kasone were added and stirred evenly. A third fat-liquor active ingredient is obtained.
(4)将第一加脂活性组分50g、第二加脂活性组分5g和第三加脂活性组分5g加入到反应设备，升温到90℃，加入脂肪醇聚氧乙烯醚琥珀酸单酯磺酸盐10份和2-甲基-2,4-戊二醇5份，搅拌60min，缓慢加入蒸馏水50g，温度保持在60℃搅拌均匀，得到合成加脂剂。(4) Add 50 g of the first fat-liquor active component, 5 g of the second fat-liquor active component, and 5 g of the third fat-liquor active component into the reaction equipment, raise the temperature to 90° C., add fatty alcohol polyoxyethylene ether succinic acid mono 10 parts of ester sulfonate and 5 parts of 2-methyl-2,4-pentanediol were stirred for 60 minutes, 50 g of distilled water was slowly added, and the temperature was kept at 60°C, and the mixture was evenly stirred to obtain a synthetic fatliquoring agent.
实施例2Example 2
将实施例1制备的第一加脂活性组分15g、实施例1制备的第二加脂活性组分25g和实施例1制备的第三加脂活性组分25g加入到反应设备，升温到70℃，加入辛癸基葡糖苷5g和乙二醇甲醚15g，搅拌60min，缓慢加入蒸馏水100g，温度保持在50℃，搅拌均匀，得到合成加脂剂。The first fatliquoring active component 15g prepared in Example 1, the second fatliquoring active component 25g prepared in Example 1 and the third fatliquoring active component 25g prepared in Example 1 were added to the reaction equipment, and the temperature was raised to 70 ℃, add 5 g of octadecyl glucoside and 15 g of ethylene glycol methyl ether, stir for 60 minutes, slowly add 100 g of distilled water, keep the temperature at 50 ℃, and stir evenly to obtain a synthetic fatliquoring agent.
实施例3Example 3
将实施例1制备的第一加脂活性组分30g、实施例1制备的第二加脂活性组分20g和实施例1制备的第三加脂活性组分20g加入到反应设备，升温到75℃，加入脂肪醇聚氧乙烯醚磷酸酯4g、烷基马来酸单酯盐3g和1,3丙二醇10g，搅拌60min，缓慢加入蒸馏水87g，温度保持在55℃，搅拌均匀，得到合成加脂剂。The first fatliquoring active component 30g prepared in Example 1, the second fatliquoring active component 20g prepared in Example 1 and the third fatliquoring active component 20g prepared in Example 1 were added to the reaction equipment, and the temperature was raised to 75 ℃, add 4g of fatty alcohol polyoxyethylene ether phosphate, 3g of alkyl maleic acid monoester salt and 10g of 1,3 propylene glycol, stir for 60min, slowly add 87g of distilled water, keep the temperature at 55℃, stir evenly to obtain synthetic fatliquoring agent.
实施例4Example 4
将实施例1制备的第一加脂活性组分20g、实施例1制备的第二加脂活性组分20g和实施例1制备的第三加脂活性组分20g加入到反应设备，升温到80℃，加入脂肪醇聚氧乙烯醚8g、异辛醇聚氧乙烯醚磷酸酯7g，搅拌60min，缓慢加入蒸馏水200g，温度保持在57℃，搅拌均匀，得到合成加脂剂。The first fatliquoring active component 20g prepared in Example 1, the second fatliquoring active component 20g prepared in Example 1 and the third fatliquoring active component 20g prepared in Example 1 were added to the reaction equipment, and the temperature was raised to 80 ℃, add 8g of fatty alcohol polyoxyethylene ether and 7g of isooctyl alcohol polyoxyethylene ether phosphate, stir for 60min, slowly add 200g of distilled water, keep the temperature at 57℃, and stir evenly to obtain a synthetic fatliquoring agent.
实施例5Example 5
将实施例1制备的第一加脂活性组分45g、实施例1制备的第二加脂活性组分10g和实施例1制备的第三加脂活性组分15g加入到反应设备，升温到80℃，加入异辛醇聚氧乙烯醚磷酸酯2g、脂肪酸甲酯聚氧乙烯醚3g、脂肪酸甲酯乙氧基化物磺酸盐5g和异丙醇15g，搅拌60min，缓慢加入蒸馏水65g，温度保持在52℃，搅拌均匀，得到合成加脂剂。The first fatliquoring active component 45g prepared in Example 1, the second fatliquoring active component 10g prepared in Example 1 and the third fatliquoring active component 15g prepared in Example 1 were added to the reaction equipment, and the temperature was raised to 80 ℃, add 2g of isooctyl alcohol polyoxyethylene ether phosphate, 3g of fatty acid methyl ester polyoxyethylene ether, 5g of fatty acid methyl ester ethoxylate sulfonate and 15g of isopropanol, stir for 60min, slowly add 65g of distilled water, and keep the temperature Stir evenly at 52°C to obtain a synthetic fatliquoring agent.
对比例1Comparative example 1
合成加脂剂LUTAPOL GLH，齐河力厚化工有限公司生产。Synthetic fatliquor LUTAPOL GLH, produced by Qihe Lihou Chemical Co., Ltd.
应用例Application example
取牛皮蓝湿革相同部位6块(每块约400g)，加入0.2％脱脂剂FB(齐河力厚化工有限公司)、0.5％草酸，在40℃条件下转2h，排水后，补水100％，加4％铬粉复鞣鞣制6h，排水后，加入1.2％小苏打和1％甲酸钠进行中和，排水后进入加脂工序，加脂工序中分别加入15％合成加脂剂(其中，合成加脂剂分别为实施例1～5制备的合成加脂剂、对比例1的合成加脂剂LUTAPOL GLH)，在50℃条件下于转鼓中处理1.5h，然后加入蓝湿皮质量1.2％的甲酸进行固定，其中，甲酸用三倍甲酸质量的水稀释后，分三次加入，每次间隔10min，水洗后取出，在70℃、100kPa条件下真空干燥10min，测试处理后的皮革的性能，其中，柔软度采用皮革柔软度测试仪DY-4023进行测试，抗撕力采用电子拉力试验机WDW-50M进行测试，吸收率＝加脂开始时加脂液中COD浓度/加脂结束时加脂液中COD浓度×100％，表面手感由制革工程师主观评价，结果如表1所示。以上质量百分数均以蓝湿皮质量计。Take 6 pieces of the same part of cowhide wet blue leather (about 400g each), add 0.2% degreasing agent FB (Qihe Lihou Chemical Co., Ltd.), 0.5% oxalic acid, and turn for 2 hours at 40°C. After draining, add water to 100% , add 4% chrome powder retanning tanning 6h, after draining, add 1.2% sodium bicarbonate and 1% sodium formate to neutralize, enter fatliquoring process after draining, add 15% synthetic fatliquor respectively in the fatliquoring process (wherein, synthetic The fatliquor is respectively the synthetic fatliquor prepared in Examples 1 to 5 and the synthetic fatliquor LUTAPOL (GLH) of Comparative Example 1, which is treated in a drum at 50°C for 1.5h, and then 1.2% of the wet blue hide quality is added The formic acid was fixed, wherein, after the formic acid was diluted with water of three times the formic acid quality, it was added in three times, with an interval of 10 minutes between each time, it was taken out after washing, and it was vacuum-dried at 70°C and 100kPa for 10 minutes, and the performance of the treated leather was tested. Among them, the softness is tested by leather softness tester DY-4023, and the tear resistance is tested by electronic tensile tester WDW-50M. Absorption rate = COD concentration in fatliquoring solution at the beginning of fatliquoring / fatliquoring at the end of fatliquoring The concentration of COD in the liquid × 100%, and the surface feel was subjectively evaluated by tannery engineers, and the results are shown in Table 1. The above mass percentages are based on the mass of wet blue leather.
表1实施例1～5和对比例1的合成加脂剂的加脂效果The fatliquoring effect of the synthetic fatliquor of table 1 embodiment 1～5 and comparative example 1
由表1可知，本发明提供的合成加脂剂后的处理皮革的柔软度在7.796以上，表面手感油润，抗撕力在66.91N以上，吸收率在90％以上，说明，本发明提供的合成加脂剂能够提高皮革的柔软度和抗撕力，且皮革对于本发明提高的合成加脂剂的吸收率高，加脂效果比对比例1的合成加脂剂LUTAPOL GLH效果优异。As can be seen from Table 1, the softness of the processed leather after the synthetic fatliquoring agent provided by the present invention is more than 7.796, the surface feels oily, the tear resistance is more than 66.91N, and the absorption rate is more than 90%. The synthetic fatliquoring agent can improve the softness and tear resistance of leather, and the leather has a high absorption rate for the synthetic fatliquoring agent improved by the present invention, and the fatliquoring effect is better than that of the synthetic fatliquoring agent LUTAPOL GLH in Comparative Example 1.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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